JPS6354025B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a mixed dye composition. More specifically, the present invention relates to the general formula () (In the formula, Z is a hydrogen atom or a lower alkoxy group,
R represents a hydrogen atom, a phenyl group, or a lower alkyl group) by simultaneously alkylating one or more compounds represented by the formula with two or more alkylating agents having a carbon number ranging from 1 to 10, N in general formula ()
-obtain an alkylated mixture and then the general formula () (In the formula, X represents a hydrogen atom, a cyano group, a chlorine atom, a bromine atom, or an iodine atom, and Y represents a cyano group or a nitro group.) Coupling with one or more diazotized compounds of the following formula [However, Compounds represented by the above general formula () in which R is a methyl group and Z is a hydrogen atom, and those having 2 and 3 carbon atoms
An N-alkylation mixture with two types of alkylating agents, and a compound represented by the general formula ()
is a chlorine atom or a bromine atom, and coupling with a compound in which Y is a cyano group is excluded] (In the formula, X, Y, Z, R represent the above meanings,
A and B each independently represent a group of two or more alkyl groups having 1 to 10 carbon atoms. Conventionally, in the field of disperse dyes, structurally similar dyes are often mixed and used in order to improve the dyeing properties of a single dye. However, even with such a method, the desired improvement in dyeability is often not achieved. The present inventors have made extensive studies to solve the above-mentioned problems in the field of azo disperse dyes, and have found that using the mixed dye composition obtained by the method of the present invention can solve these problems. I have found that this can be solved all at once. The mixed dye composition of the present invention can dye polyester fibers and polyester/cellulose mixed products in a deep purple to dark green-blue color,
It has the characteristics of high dyeability, good build-up properties, and high coloring power. In addition, the obtained dyed product has excellent various fastnesses, such as sunlight fastness, wet fastness (water fastness, washing fastness), rubbing fastness, and sublimation fastness. Furthermore, when dyeing a polyester/cellulose mixed product, there is little contamination of the cellulose portion and the absorbency is excellent. Furthermore, it is noteworthy that the mixed dye of the present invention has better exhaustion and build-up properties than each dye alone or a dye obtained by separately synthesizing and mixing them. Furthermore, the present invention has the advantage that there is no need for separate manufacturing and blending operations, and that it is easy to atomize the components during commercialization. The mixed dye composition of the present invention can be produced as follows. One or two of the compounds represented by the general formula () are alkylated simultaneously using two or more alkylating agents in the presence of a deoxidizing agent by a method known per se.
More than one type of N-alkylated product is obtained. Add this to hydrochloric acid,
A coupling component is obtained by dissolving or suspending in a mineral acid such as sulfuric acid, an organic acid such as acetic acid or propionic acid, or an organic solvent such as methanol or ethanol. On the other hand, one or more amine compounds represented by the general formula () can be used as is, or with sulfuric acid,
After dissolving or suspending it in a mineral acid such as hydrochloric acid or an organic acid such as acetic acid or propionic acid, it is reacted with nitrosyl sulfuric acid at 0 to 50°C for 2 to 5 hours to form a diazonium solution. This diazonium liquid is added dropwise to the coupling component when cold, preferably at 10°C or below, and then
- React for 10 hours to complete coupling.
After the reaction is completed, the precipitated product is separated, washed with water, and dried to obtain a mixture of monoazo dyes represented by the general formula (). In the present invention, an alkylating agent having 1 to 10 carbon atoms means that the alkyl group to be alkylated has 1 carbon number.
-10, and two or more of these must be used in combination. Specific examples of the alkylating agent include alkyl esters of sulfuric acid such as dimethyl sulfate and diethyl sulfate, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, and p-toluenesulfonic acid ethyl ester.
- Alkyl esters of p-toluenesulfonic acid such as toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, methyl iodide, ethyl iodide, propyl bromide, butyl bromide, amyl bromide, hexyl bromide, heptyl bromide,
Examples include alkyl halides such as octyl bromide, nonyl bromide, decyl bromide, amyl chloride, hexyl chloride, and heptyl chloride. As a deoxidizing agent, soda carbonate, potassium carbonate,
Salts such as calcium carbonate, magnesium carbonate, and bicarbonate of soda are used. Examples of the compound represented by the general formula () include 2,4-dinitroaniline, 2-cyano-4
-Nitroaniline, 2-cyano-4,6-dinitroaniline, 2,6-dicyano-4-nitroaniline, 2-chloro-4-nitro-6-cyanoaniline, 2-chloro-4,6-dinitroaniline,
2-bromo-4-nitro-6-cyanoaniline,
One or two of 2-bromo-4,6-dinitroaniline, 2-iodo-4-nitro-6-cyanoaniline, and 2-iodo-4,6-dinitroaniline
Examples include mixtures of more than one species. Examples of the compound represented by the general formula () include one or a mixture of two or more of the following compounds. 3-formylaminoaniline, 3-acetylaminoaniline, 3-propionylaminoaniline, 3-butyrylaminoaniline, 3-pentanoylaminoaniline, 3-benzoylaminoaniline, 2-methoxy-5-acetylaminoaniline, 2- Methoxy-5-formylaminoaniline, 2-methoxy-5-propionylaminoaniline, 2-methoxy-5-butyrylaminoaniline, 2-methoxy-5-pentanoylaminoaniline, 2-methoxy-5-benzoylaminoaniline, 2-ethoxy-5-formylaminoaniline, 2-ethoxy-5-acetylaminoaniline, 2-ethoxy-5-propionylaminoaniline, 2-ethoxy-5-butyrylaminoaniline, 2-ethoxy-5-pentanoylamino Aniline, 2-ethoxy-5-benzoylaminoaniline, 2-propoxy-5-acetylaminoaniline, 2-propoxy-5-propionylaminoaniline, 2-butoxy-5-formylaminoaniline, 2-butoxy-5-acetylaminoaniline Aniline In the general formula (), A and B each independently represent two or more alkyl group groups that are the same or different. For example, if the alkylating agent is 2
type, the obtained N-alkylated mixture of general formula () is the general formula (-1), (-2) and (-3). (In the formula, R ₁ and R ₂ represent different alkyl groups having 1 to 10 carbon atoms.) Therefore, the mixed dyes of the general formula () obtained are (-1), (-2) and (-
3) It is a mixture of At this time, A is R ₁ and R ₂ and B is
Represents R ₁ and R ₂ . To carry out dyeing using the mixed dye of the present invention, the mixed dye represented by the general formula () is ground and dispersed into fine particles in an aqueous medium together with a suitable dispersant. Dispersed dyes can be used in paste form, or
Alternatively, it can be used in powder form by spray drying or the like. Using the dye composition thus obtained, polyester fibers are immersed in an aqueous medium and dyed under pressure at 105°C or higher, preferably from 110 to 140°C. It is also possible to dye at relatively high temperatures, for example at boiling water, in the presence of a carrier such as o-phenylphenol or trichlorobenzene. Furthermore, it is also possible to perform so-called thermosol dyeing, in which a dye composition dispersion is padded onto cloth and subjected to dry heat treatment at 150 to 230°C for 30 to 120 seconds. On the other hand, in the case of textile printing, the dye composition is adjusted to the desired concentration and viscosity using a suitable thickening agent, and then printed onto the object to be dyed, and dyed by steaming or thermosol treatment. When dyeing polyester/cellulose blends, this is carried out in combination with suitable dyes for cellulose. Particular preference is given to the combination with reactive dyes, which can be carried out, for example, as follows. A dye is prepared by mixing the dye composition of the present invention with an appropriate reactive dye, and a polyester/cellulose mixture is immersed in the dye to adjust the desired squeezing ratio. After drying, steaming or thermosol treatment is performed. to fix the disperse dye to the polyester part.
Next, an alkaline aqueous solution is applied thereto, and if necessary, a heat treatment such as steaming is performed to fix the reactive dye to the cellulose portion. According to the mixed dye of the present invention, polyester fibers and polyester/cellulose mixed products can be dyed in deep purple to greenish-blue colors, and the dyed products have excellent color fastness, and their industrial value is extremely large. It is something. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In the examples, parts represent parts by weight, and % represents weight %. Example 1 150 parts of 3-acetyl group aminoaniline was reacted with 151 parts of amyl bromide, 165 parts of hexyl bromide, and 106 parts of anhydrous sodium carbonate at 120 to 130°C for 4 hours to obtain an alkylated mixture. This mixture was dissolved in 1000 parts of methanol to form a coupling component. On the other hand, 197.5 parts of 2-chloro-4-nitro-6-chloroaniline was added to 0-10
Diazotization was carried out at a temperature of 0.degree. C., and the resulting diazo solution was added dropwise to the coupling component at a temperature of 5.degree. C. or below to carry out a coupling reaction. After coupling, separate the product,
Washed with water and dried. 573 parts of mixed dye composition were obtained. The DMF λmax of this dye composition is 600 nm. Reference Example 1 2 parts of the mixed dye composition of Example 1 was added to naphthalene.
The mixture is atomized and dispersed together with 2 parts of a formalin condensate of β-sulfonic acid and 1 part of sodium ligninsulfonate, and this and 3 parts of higher alcohol sulfate are uniformly dispersed in 3000 parts of water to prepare a dye bath. 100 parts of Tetoron spun yarn (polyester fiber; manufactured by Toray Industries, Inc.) was immersed in this dye bath, and dyed at 130°C for 60 minutes. Reduction cleaning treatment is performed at 85°C for 10 minutes with a treatment solution consisting of 3 parts of surfactant and 3000 parts of water. Then wash with water and dry. A deep, vivid and solid royal blue dyeing was obtained. Example 2 2-methoxy-5-acetylaminoaniline
180 parts with 126 parts of dimethyl sulfate, 154 parts of diethyl sulfate and 138 parts of anhydrous potassium carbonate, 95-100 parts
The alkylation mixture was obtained by reacting at ℃ for 5 hours.
This mixture was dissolved in 1000 parts of dilute sulfuric acid to prepare a coupling component. On the other hand, 2-chloro-4,6-dinitroaniline
217.5 parts were diazotized using nitrosyl sulfuric acid at 30 to 40°C, and the diazo solution was added dropwise to the coupling component at 5°C or lower to perform a coupling reaction. After the coupling was completed, the product was separated, washed with water, and dried to obtain 396 parts of a mixed dye composition.
The λmax of this dye composition in DMF was 625 nm. Reference Example 2 When dyeing was carried out in the same manner as in Reference Example 1 using the dye composition of Example 2, a dyed product of a strong blue color with high density was obtained. Example 3 90 parts of 3-acetylaminoaniline and 72 parts of 2-methoxy-5-acetylaminoaniline were mixed with p-
200 parts of toluenesulfonic acid ethyl ester, p-
An alkylated mixed composition was obtained by reacting with 214 parts of toluenesulfonic acid propyl ester and 168 parts of sodium bicarbonate at 95-105°C for 5 hours. This mixed composition is dissolved in 1000 parts of dilute sulfuric acid to prepare a coupling component. On the other hand, 2-bromo-4,6-dinitroaniline
262 parts were diazotized with nitrosyl sulfuric acid, and the diazo solution was added dropwise to the coupling component at 5° C. or lower to carry out a coupling reaction. After the coupling was completed, the product was separated, washed with water, and dried. 455 parts of dye composition were obtained. The λmax of this dye composition in DMF was 592 nm. Reference Example 3 2 parts of the dye composition of Example 3 was added to naphthalene-β-
Atomize and disperse with 2 parts of formalin condensate of sulfonic acid, and add water to make a dispersion with a dye content of 10%.
Using this dispersion liquid, a padding liquid is prepared with the following composition. Dye dispersion 8 parts Sodium alginate (1 part) 10 parts Water 82 parts The above padding solution was padded onto a polyester/cellulose blend poplin cloth, and the squeezing rate was
After adjusting to 60%, dry at 110℃ for 30 seconds. Then thermosol treatment is performed at 210°C for 60 seconds. Washed in hot water, treated in a solution containing 2 g of Neugen HC (nonionic surfactant; Daiichi Kogyo Seiyaku Co., Ltd.) at 80°C for 30 seconds, washed with cold water, and then dried. did. The polyester part of this mixed product is dyed a deep navy blue,
Almost no contamination of the cellulose portion was observed. Thereafter, a dye composition was synthesized in the same manner as in Example 1, and polyester fibers were dyed using the dye composition in the same manner as in Reference Example 1. The results shown in Table 1 were obtained.

【table】

[Table] Example 13 75 parts of 3-acetylaminoaniline and 90 parts of 2-methoxy-5-acetylaminoaniline were mixed with p-
230 parts of toluenesulfonic acid butyl ester, p-
An alkylated mixed composition was obtained by reacting with 214 parts of toluenesulfonic acid propyl ester and 168 parts of sodium bicarbonate at 95-105°C for 5 hours. This mixed composition is dissolved in 1000 parts of dilute sulfuric acid to prepare a coupling component. On the other hand, 2-bromo-4,6-dinitroaniline
262 parts were diazotized with nitrosyl sulfuric acid, and the diazo solution was added dropwise to the coupling component at 5° C. or below to perform a coupling reaction. After the coupling was completed, the product was separated, washed with water, and dried. 455 parts of dye composition were obtained. Thereafter, the following mixed dye was synthesized in the same manner as in Example 13, and polyester fibers were dyed in the same manner as in Reference Example 1 using the obtained mixed dye. The results shown in Table 2 were obtained.

【table】

【table】

Claims (1)

[Claims] 1 General formula () (In the formula, Z is a hydrogen atom or a lower alkoxy group,
R represents a hydrogen atom, a phenyl group, or a lower alkyl group) by simultaneously alkylating one or more compounds represented by the formula with two or more alkylating agents having a carbon number ranging from 1 to 10, N in general formula ()
-obtain an alkylated mixture and then the general formula () (In the formula, X represents a hydrogen atom, a cyano group, a chlorine atom, a bromine atom, or an iodine atom, and Y represents a cyano group or a nitro group.) Coupling with one or more diazotized compounds of the following formula [However, Compounds represented by the above general formula () in which R is a methyl group and Z is a hydrogen atom, and those having 2 and 3 carbon atoms
An N-alkylation mixture with two types of alkylating agents, and a compound represented by the general formula ()
is a chlorine atom or a bromine atom, and coupling with a compound in which Y is a cyano group is excluded] (In the formula, X, Y, Z, R represent the above meanings,
A and B each independently represent two or more alkyl groups having 1 to 10 carbon atoms.